New metal complex dyestuffs



NEW METAL COMPLEX DYESTUFFS Hans Ruprecht Hensel, Heidelberg, Bemd Eistert, Saarbruecken, and Hans Baiimann and Johannes Delrnert, Ludwigshafen (Rhine), Germany, assignors to Badische Anilin- & Soda-Fabrik Aktiengesellschaft, Ludwigshafen (Rhine), Germany No Drawing. Application April 22, 1958 1 Serial No. 730,062

This invention relates to new metal compounds and I especially it relates to new metallized dyestuifs of great value in the field of the dyeing of textiles, of lacquers, plastics and so on.

We have found that new metal complex dyestufis are with at least one primary aromatic amino compound which contains a hydroxyl or thiol group in ortho-position to the amino group and reacting the resultant dianils of the tautomeric formulae R R CH=I!I oil-1 R-N=NC R-N=NO in CH=N GH=N RI! II wherein R represents an aromatic radical and R and R" aromatic radicals which are identical with or diflerent from each other and which contain a hydroxyl or thiol group in ortho-position to the nitrogen atom with a metalsupplying compound of a complex-forming metal;

For the sake of simplicity, only the right-hand of the above two tautomeric formulae will be used hereinafter.

The arylazo-malonodialdehydes used as initial materials for the new process have the general formula:

in which R is an aromatic radical. They can readily be obtained for example by coupling any diazonium salts with beta-aminoacroleins twice substituted on the nitrogen atom. Like the aromatic ortho-aminohydroxyl or orthoaminothiol compounds, they may also contain substantially neutral substituents, such as halogen atoms, sulfonic acid, carboxylic acid, sulfonic acid or carboxylic acid amido, alkyl sulfone, aryl sulfone, aryl azo, alkoxy, nitro or acylamino groups; these groups may be further halides, sulfates or nitrates of the so-called transition as Q 3? metals of the atomic numbers 24 to 30, for example of copper, nickel, cobalt, iron, zinc or chromium; the complexes of these metals for example with salicylic acid or with other compounds capable of forming chelates may however also be used as metal-supplying compounds.

The reaction .of the arylazo-malonodialdehydes with the aromatic ortho-aminohydroxyl or ortho-aminothiol compounds may be carried out for example by dissolving the two said reactants water or in organictsolvents, as for example alcohols, acetone, glacial acetic acid, formamide,

dimethyl-formamide, diglycol or pyridine, in about the obtained by condensing an arylazo-malonodialdehyde r;

2,920,071 i Patented Jan. 5-, 1960 ice . 2 mol ratio 1:2 of the reactants, and allowing them to react in the solution at a temperature of about 20 to 100 C., preferably at to C., for a period of 20 to 30 minutes. 'It is not necessary that the amount of the but a smaller amount of the solvent dissolving the reactants partly will do. It is possible however to react 1 mol of the arylazo-malonodialdehyde simultaneously or consecutively with 1 mol each of ortho-aminohydroxyl 0 and/or ortho-aminothiol compounds which are difierent from each other, thus arriving at di-anils of the above formula in which R and R" are difierent from each other, Then at least lmol of a compound of acomplex-forming metal is added, whereupon, depending on the nature of the solvent and of the substituents in'the aromatic radicals of the dyestufi, the latter is precipitated in crystalline form either while still hot or after allowing to cool, or is separated by thesubsequent addition of a precipitant, such as water, acetone alcohol or sodium chloride solution. A variant of the process characterized by special simplicity comprises allowing all the reaction componentsarylazo-malonodialdehyde, aromatic ortho-aminohydroxyl and/or ortho-aminothiol compounds and a compound of a complex-forming meta1to react on one another, either at ordinary or elevated temperature, a period of from one quarter of an hour to six hours, but usually between one half hour and four hours, being necessary for complete reaction.

The nature ofthe substituents in the aromatic radicals of the reactants influences the shade of color, the solubility and the fastness properties of the complex dyestuffs. For example especially deep shades of color are obtained when using'for the new process arylazomalonodialdehydes prepared by coupling 4-aminoazobenzene and similar compounds with a beta-dialkylamino-acrolein.

The new dyestuffs are suitable for dyeing and coloring lacquers, plastics and natural and synthetic fibers, especially wool, silk and synthetic polyamide fibers, as for example polycaprolactam and polyhexamethylenediamine adipate, on which they give dyeings of good to excellent fastness to light and good to very good wet fastness properties.

The following examples willffurther illustrate this invention but the invention is not restricted to these examples but in particular extends, to many more dyestuffs.

I Example 1 HnNOzl 1" N on \H HzNOzS The dyestuff dyes, wool and polyamide fibers orangeyellow shades from anacid bath.

solvent is sufficient to dissolve the reactants completely,-

The parts specified in the examples are parts by weight.

.3 Example 2 HgCsHNOa? o1 I l HBCQHNOIS and dyes wool and polyamide fibers orange to brown shades from an acid bath.

Instead of using the above-mentioned azo-malonodialdehyde compound of 2.5-dichlorobenzene, the reaction may also be carried out for example with those of alphaor beta-naphthylamine, of 1-aminonaphthalene-4-sulfonic acid or of 2-aminonaphthalene-6-sulfonic acid dimethylamide.

Example 3 11 parts of a dyestutf which dyes wool and polyamide fibers Bordeaux red to violet shades from a neutral or weak acid bath are obtained from 4.4 parts of 4-nitrophenylazo-malonodialdehyde, 9.1 parts of 1-hydroxy-2- aminobenzene-4-sulfonic acid dimethylarnide in 200 parts of dimethylformamide and a solution of 5 parts of crystallized copper sulfate in 50 parts of water by the technique described in Example 1.

Example 4 From 6.8 parts of benzene-4-sulfonic acid-1(azo)4- benzene-1(azo)2-malonodialdehyde, 5.7 parts of l-hy- -droxyl-Z-amino-4-chlorbenzene there are obtained as in Example 1 by using a solution of 5 parts of crystallized copper sulfate in 50 parts of water, 12 parts of the copper complex of the di-anil of the formula It dyes wool or polyamide fibers violet shades from an acid bath.

Example 5 4.2 parts of para-chlorphenylazo-malonodialdehyde and 14 parts of 1-hydroxy-2-amino-4-nitrobenzene-6-sulfonic acid are heated in 150 parts of dimethylformamide for 30 minutes at 80 C. and then a solution of 5 parts of crystallized copper sulfate in 50 parts of water is added V 4 v to the mixture. 18 parts of the copper complex of the di-anil of the formula are obtained. It dyes wool and polyamide fibers orange shades from a neutral to acid bath.

Example 6 From 4.4 parts of 4-m'trophenylazo-malonodialdehyde and 13.6 parts of 1-amino-2-hydroxynaphthalene-4-sulfonic acid in 200 parts of dimethylformamide there are obtained, after the addition of a solution of 5 parts of nickel acetate in 20 parts of Water, 11 parts of the nickel complex of the di-anil of the formula SOaH It dyes wool and polyamide fibers brown-red shades from a neutral to acid bath.

Example 17 From 5.1 parts of benzene-l-azornalonodialdehyde-4- sulfonic acid amide and 5 parts of 2-aminothiophenol in parts of dimethylformamide there are obtained, after the addition of a solution of 5 parts of copper sulfate in 30 parts of water, 12 parts of a dyestufl consisting of the copper complex of the di-anil of the formula l N s13 N SE which dyes wool and polyamide-fibers brown shades from an acid bath.-

From 1 mol of the arylazo-malonodialdehyde component specified in paragraph 1 of this example and 2 mols of 1-hydroxy-2-amino-4-nitrobenzene, there may be obtained as describedin the said paragraph 1 the copper complex of the di-anil of the formula On r Similarly 2 mols of 1-hydroxy-Z-amino-S-nitrobenzene or 1 mol each of l-hydroxy-2-amino-4- and -5-nitrobenzene may be used.

Example 8 there are obtained 10 parts of the zinc complex of the di-anil of the formula 7 110, p, t t and which dyes wool and polyamide fibers Bordeaux red shades from a neutral to acid bath.

Example 9 From a mixture of 11 parts of benzene-'l(azo)4-benzene-l(azo)2-malonodialdehyde, 15.5 parts of l-amino- 2-hydroxy-benzene-5-sulfonic acid amide and '200 parts v of dimethylformamide there is obtained, by adding 11 parts of crystallized chromium (III) chloride and heat; ing for 1 hour at 120 to 130 C., a violet dyestufi which consists of the chromium complex of the di-anil of the formula I 112N013 in an amount of 20 parts. It dyes wool and polyamide fibers violet shades from a neutral to acid bath.

Example 10 A mixture of 9 parts of 4-nitrophenylazo-malonodialdehyde, 15.5 parts of 1-amino-2-hydroxybenzene-5-sulfonic acid amide, 10 parts of cobalt (II) acetate and 250 parts of dimethylformamide is heated for 4 hours at 120 to 130 C. and there are thus obtained 22 parts of the cobalt complex of the di-anil of the formula Emma It dyes wool and polyamide fibers Bordeaux red shades fromaneutral toacidbath. v

Example 11 A mixture of 5.1 parts of benzene-l-sulfonic acid amide-47(azo)2-malonodialdehyde, 7.6 parts of l aminoacetate and 150 parts of dimcthylformamide is heated for 1 hour at 120 to 130 C. After dilution with water It dyes wool and polyamide fibers orange shades from a neutral bath. f

Example 12 'From a mixture of 4.4 parts of 4-nitrophenylazomalonodialdehyde, 6.8 parts of l-amino 2-hydroxy-4-nitrobenzene, 3.6 parts of zinc acetate and 200 parts of dimethylformamide there are obtained after heating for an hour 9 parts of the zinc complex of the di-anil of the formula It dyes wool Bordeaux red shades. and polyamide fibers blue shades from a neutral to weak acid bath.

' Example 13 10 parts of 2.5-dichlorphenylazo-malonodialdehyde, 8 parts of 1-hydroxy-2-aminobenzene-4-sulfonic acid amide and 10 parts of 1-hydroxy-2-aminobenzene-4-sulfonic acid anilide are dissolved in 250 parts of dimethylformamide while heating to to 70 C. Then a solution of 10 parts of crystallized'copper sulfate in 100 parts of water is added and the complex dyestufi, after the reaction mixture has been stirred for another hour at 50 to Y 7 0 C., precipitated by the addition of 300 parts of water.

The yield amounts to 25 parts of the copper complex of the di-anil of the formula It dyes wool and polyamide fibers orange shades.

W Example 14" l 100 parts of woolen fabric are'introduced at 50 C. into a dyebath which contains,:in 4000 parts of water,

I V l p A UN part of the dyestufi of Example 2, 1 part of the reac- 2-hydroxybenzen-5-sulfonic acid amide, 3.6 parts of zinc j '7 and 3 parts of 30% acetic acid. The bath is heated during the course of 20 minutes to 98 to 100 C. and dyeing continued for 5.0 minutes at this temperature. An orange dyeing of good uniformity, excellent fastness to light and very good wet fastness properties is thus tained from 1 mol of sperm oil alcohol by adding on 80 mole of ethylene oxide and by sulfonation of the addition. product, in 5000 parts of Water. The bath is heated during the course of 30'minutes to 100 C., then 10 parts of ammonium sulfate are introduced, and the 0 b i d, said temperature is maintained for about 30 to 60 min- Example 15 utes. A red-brown dyeing of excellent fastness to light and very good wet fastness properties is obtained.

Parts of a woven f'q a 9 The following table gives components suitable for the as for p e polyhexamethylenedlamme a a or 10 production of. further dyestufis of the said kind by the Polycapl'olactamkf of a Polyurethane: are mtmduced methods of Examples 1 to 13; the complexes obtainable Into a bath: at Of 2 Parts of the dyestufi of Example therefrom with compounds of the said metals may be used Paragraph 2, 5 to 10 Parts of 25% aqueous ammonla for dyeing wool or polyamide fibers by the methods of solution, and 5 to 10 parts of the reaction product ob- Examples 13 and 14.

Shade of color onaromatic orthohydroxyl erylazomalonodialdehyde component (1 mol) component (2 mols) metal wool polyamide bers OH 1-11YdmY-2-amimbemne-- {fifilglifaaiii fifi fifaeaiii: 333%.... O

0H l-hydroxy-Z-aminobenzene- {copper orange orange. N=N 4-sulfon1c acid amide. chromium.-. red-brown red-brown.

OH l-hydroxy-Z-aminobenzene- {copper orange orange. 4-su1fon1cac1d amlide. chromium... red-brown red-brown.

l-hydroxyQ-aminobenzane- {copper orange orange.

4-carboxylic acid amide. chromium-.. red-brown red-brown.

l-hydroxy-Z-amino--nitro- {copper reddish orange.. reddishorange.

benzene. chromium... brown-red brown-red.

copper..- brown brown. 1-hydroxy-2-aminobenzenechromium... Bordeaux Bordeaux. 4-sulfonic acid. cobalt Bordeaux Bordeaux.

copper l-hydroxy-Z-aminmS-nitrochromium.-. Bordeaux blue.

benzene. zinc 1-hydroxy-2-aminobenzeneorange orange.

4-sullonic acid dimethylred-brown red-brown. amide. orange orange.

l-hydroxy-2-amino-4-chloro- {copper orange orange.

benzene. chromium... red-brown red-brown.

l-hydrbxy-Z-amino-fi-nitrm copper red-brown red-brown.

benzene. chromium... brown-violet brown-violet.

e-sult'onic acid.

a F I Shadeotcoloronaromatic orthohydroxyl arylazomalonodleldehyde component (1 mol) component (2 mols) metal E i. wool pol ide .V v v copper reddish orange reddishorange. 1-hydroxy-2-aminobenzenechromium... red-brown red-brown.

e-sultonie acid anllide. zinc reddish orange reddishorange.

l-hydroxy-Z-aminobenzene- {copper red-brownred-brown.

chromium..- violet violet.

d-sulionle acid amide.

J 1hd 2 i suit i riii -yro --amno-- roco um- Q Q benzeiig. zinc I t 0H l-hydroxy-z-aminobenzene- {copper red-brown red-brown- H|N0;8 N=N N=N- 4-su1ionlc;acl,dnnillde.fl chromium... violet. violet.

OCH:

0H l-hydroxy-z-amlno-li-nitro- {copper... brown brown. H|NO:|S N=N N=N- benzene. chromium.-. violet violet.

We claim: consisting of copper, nickel, cobalt, iron, zinc and 1. -A process for the production 'of'metalcomplex dyestufis which comprises condensing a member selected from the group consisting of a benzeneazo-malono'dialdehyde, ben'zenea'zo-benzeneazo-malonodialdehyde and a naphthaleneazo-malonodialdehyde with a-pr imary aromatic amino compound selected from the group consisting of a primary aniline and a primary naphthyl amine, said amino compound containing a member selected from the group consisting of a hydroxy and a thiol group in ortho-position to the nitrogen atom, and reacting the di-anil thus formed with a' metal-supplying compound of a complex-formingmetal selected from the group consisting of copper, nickel, cobalt, iron, zinc and chromium.

2. A metal complex compound consisting of a di-anil of the formula mediums;-

and of a complex-forming metal selected from the group chromium.

4. A metal complex compound consisting of a di-anil of the formula r HlNOflS and of a complex-forming metal selected from the group consisting of copper, nickel, cobalt, iron, zinc and chromium.

. 5. A metal complex compound consisting of a di-anil of the formula memos ntctmiozs and of a complex-forming metal selected from the group consisting ,gf copper, nickel, cobalt, iron, zinc and chromium.

6. A metal complex compound consisting of a di-anil of'theformulag 2 iNOzS mums and of a complex-forming metal selected from the group 11. A metal complexcompound consisting of a di-anil consisting of copper, nickel, cobalt, iron, zinc and of the formula chromium. H.018;

7. A metal complex compound consisting of a di-anil of the formula HOtS and of a complex-forming metal selected from the group .consisting of copper, nickel, cobalt, Iron, zinc and C1" chromium. and of a complex-forming metal selected from the group A metal complex comPmmd conslstmg a dl'aml consisting of copper, nickel, cobalt, iron, zinc and of the formula chromium. 151N018 8. A metal complex compound consisting of a di-anil of the formula Errors 30 and of a complex-forming: metal selected from the group consisting of copper, nickel, cobalt, iron, zinc and 0N chromium.

and of a complex-forming metal selected from the group h; 2 32" complex'wmpwnd'conslstmg dl-aml consisting of copper, nickel, cobalt, iron, zinc and 05 HNO S chromium. 7

9. A metal complex compound consisting of a di-anil I of the formula a N. on

N on mNois--N=N H I and of a complex-forming metal selected from the group and of a complex-formingmetal select'ed'fro'm-the' group consisting of copper, nickel, cobalt, iron, zinc and consisting of copper, nickel, cobalt, iron, zinc and chromium.

chromium. 5o 14. A metal complex compound consisting of a di-anil 10. A metal complex compound consisting of a di-anil of the formula of the formula H=N 0,8

mcumom 0N and 0fi a complex-forming metal selected from the group and of a complex-forming metal selected from the group consmmg of copper mckel cobalt Zmc and consisting of copper, nickel, cobalt, iron, zinc and chrommm' chromium. No-references cited. 

1. A PROCESS FOR THE PRODUCTION OF METAL COMPLEX DYESTUFFS WHICH COMPRISES CONDENSING A MEMBER SELECTED FROM THE GROUP CONSISTING OF A BENZENEAZO-MALONODIALDEHYDE, BENZENEAZO-BENZENEAZO-MALONODIALDEHYDE AND A NAPHTHALENEAZO-MALONODIALDEHYDE WITH A PRIMARY AROMATIC AMINO COMPOUND SELECTED FROM THE GROUP CONSISTING OF A PRIMARY ANILINE AND A PRIMARY NAPHTHYL AMINE, SAID AMINO COMPOUND CONTAINING A MEMBER SELECTED FROM THE GROUP CONSISTING OF A HYDROXY AND A THIOL GROUP IN ORTHO-POSITION TO THE NITROGEN ATOM, AND REACTING THE DI-ANIL THUS FORMED WITH A METAL-SUPPLYING COMPOUND OF A COMPLEX-FORMING METAL SELECTED FROM THE GROUP CONSISTING OF COPPER, MICKEL,COBALT, ZINC CHROMIUM. 